ABINITIO STUDY OF THE INTERNAL-ROTATION BARRIER OF FORMAMIDE AND THE FORMAMIDE H2O COMPLEX

The barriers to internal rotation about the N-C bond of formamide and the formamide-H2O complex have been examined by ab initio quantum chemistry methods. Both self-consistent field and correlated approaches have been utilized to determine the geometries, energies, and local harmonic vibrational frequencies of the minimum-energy and transition-state structures of these two systems. We find that formamide's rotation barrier of 14-15 kcal/mol is increased to 16-18 kcal/mol when a single H2O molecule is attached. This result contrasts with the effect of a single H2O solvent molecule on the barrier to tautomerization of formamide (to form formamidic acid HN-CHOH) for which a barrier lowering of ca. 20 kcal/mol has been observed. The rotation barriers obtained for formamide and for its H2O complex are compared with barriers obtained experimentally in various solvents.